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Emerging Contaminants: Science and Policy(Responsible Editors: Bin Wang, Qian Sui, Haoran Wei, Damià Barceló & Gang Yu)
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  • RESEARCH ARTICLE
    Shuyan Zhou, Yang Zhang, Jingjing Wang, Shikun Cheng, Fuyan Zhuo, Yun Hong
    Frontiers of Environmental Science & Engineering, 2024, 18(4): 43. https://doi.org/10.1007/s11783-024-1803-8

    ● The situation of endosulfan residues in cotton fields were assessed.

    ● A KAP survey was carried out for cotton farmers.

    ● Endosulfan sulfate was the main endosulfan residue in the soil.

    ● Cotton farmers scored low on knowledge about the phase-out of endosulfan.

    We assessed the situation of endosulfan residues in cotton fields after the endosulfan ban came into effect and the current knowledge, attitude, and practice (KAP) of cotton farmers on the phase-out of endosulfan and the application of alternative technologies. Topsoil samples (n = 91) of cotton fields were collected from the major cotton-producing areas in China, namely the north-west inland cotton region, and the endosulfan residues were analyzed. A KAP survey was carried out for cotton farmers, and 291 questionnaires were distributed. The influences of gender, age, education background, cotton planting years, publicity and training, income sources, and other factors on cotton farmers’ KAP were analyzed. The results showed that endosulfan sulfate was the main endosulfan residue in the soil, followed by β-endosulfan and α-endosulfan, the average residual contents were 0.569, 0.139, and 0.060 µg/kg, respectively. The results of the KAP study showed that cotton farmers scored low on knowledge about the phase-out of endosulfan and the application of alternative technologies but high on attitude and practice. The number of family members, years of cotton planting, age, and the cotton-planting area had different degrees of influence on KAP scores. The training could significantly improve the KAP scores of cotton farmers; training should be more targeted and designed reasonably for key groups, such as men and the population under 30, followed by training them to use pesticides safely. For large-scale cotton growers, training should focus on green prevention and control technologies.

  • PREFACE
    Bin Wang, Qian Sui, Haoran Wei, Damià Barceló, Gang Yu
    Frontiers of Environmental Science & Engineering, 2023, 17(5): 65. https://doi.org/10.1007/s11783-023-1665-5
  • REVIEW ARTICLE
    Seo Won Cho, Haoran Wei
    Frontiers of Environmental Science & Engineering, 2023, 17(5): 57. https://doi.org/10.1007/s11783-023-1657-5

    ● Definition of emerging contaminants in drinking water is introduced.

    ● SERS and standard methods for emerging contaminant analysis are compared.

    ● Enhancement factor and accessibility of SERS hot spots are equally important.

    ● SERS sensors should be tailored according to emerging contaminant properties.

    ● Challenges to meet drinking water regulatory guidelines are discussed.

    Emerging contaminants (ECs) in drinking water pose threats to public health due to their environmental prevalence and potential toxicity. The occurrence of ECs in our drinking water supplies depends on their physicochemical properties, discharging rate, and susceptibility to removal by water treatment processes. Uncertain health effects of long-term exposure to ECs justify their regular monitoring in drinking water supplies. In this review article, we will summarize the current status and future opportunities of surface-enhanced Raman spectroscopy (SERS) for EC analysis in drinking water. Working principles of SERS are first introduced and a comparison of SERS and liquid chromatography-tandem mass spectrometry in terms of cost, time, sensitivity, and availability is made. Subsequently, we discuss the strategies for designing effective SERS sensors for EC analysis based on five categories—per- and polyfluoroalkyl substances, novel pesticides, pharmaceuticals, endocrine-disrupting chemicals, and microplastics. In addition to maximizing the intrinsic enhancement factors of SERS substrates, strategies to improve hot spot accessibilities to the targeting ECs are equally important. This is a review article focusing on SERS analysis of ECs in drinking water. The discussions are not only guided by numerous endeavors to advance SERS technology but also by the drinking water regulatory policy.

  • VIEWS
    Han Qu, Hongting Diao, Jiajun Han, Bin Wang, Gang Yu
    Frontiers of Environmental Science & Engineering, 2023, 17(1): 12. https://doi.org/10.1007/s11783-023-1612-5

    Over the past decades, the plastic production has been dramatically increased. Indeed, a category of small plastic particles mainly with the shapes of fragments, fibers, or spheres, called microplastics (particles smaller than 5 mm) and nanoplastics (particles smaller than 1 μm) have attracted particular attention. Because of its wide distribution in the environment and potential adverse effects to animal and human, microplastic pollution has been reported as a serious environment problem receiving increased attention in recent years. As one of the commonly detected emerging contaminants in the environment, recent evidence indicates that the concentration of microplastics show an increasing trend, for the reason that up to 12.7 million metric tons of plastic litter is released into aquatic environment from land-based sources each year. Furthermore, microplastic exposure levels of model organisms in laboratory studies are usually several orders of magnitude higher than those found in environment, and the microplastics exposure conditions are also different with those observed in the environment. Additionally, the detection of microplastics in feces indicates that they can be excreted out of the bodies of animal and human. Hence, great uncertainties might exist in microplastics exposure and health risk assessment based on current studies, which might be exaggerated. Policies reduce microplastic emission sources and hence minimize their environmental risks are determined. To promote the above policies, we must first overcome the technical obstacles of detecting microplastics in various samples.

  • RESEARCH ARTICLE
    Yuping Wang, Jing Xia, Yanxin Gao
    Frontiers of Environmental Science & Engineering, 2022, 16(12): 154. https://doi.org/10.1007/s11783-022-1589-5

    ● A series of mixed-LOFs and portable LOF-fibers were synthesized.

    ● LOF-S3 was selected as a luminescent sensor for antibiotics.

    ● Mixed-LOF was capable of decoding antibiotics by emission intensity ratios.

    ● Linear relationship between antibiotic concentration and I545nm/I618nm was observed.

    Due to the potential risk of antibiotics to the environment, the development of inexpensive, simple, and reliable antibiotic detection methods is significant but also faces challenges. In this work, several lanthanide-organic frameworks (LOFs), constructed from lanthanide ions (Eu3+ and/or Tb3+) and 1,3,5-benzene-tricarboxylic acid (BTC), were synthesized by solvothermal method. LOF-S3 with comparable emission peaks of 5D47F5 (Tb3+, 545 nm) and 5D07F2 (Eu3+, 618 nm) was selected as a luminescent sensor. In this system, the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb3+ to Eu3+ occurs. LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios. Therefore, a two-dimensional decoded map of antibiotics was established. The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible. As a typical analyte, the response mechanism of nalidixic acid (NA) was investigated in detail. The competition of NA and BTC for UV light absorption, as well as the binding propensity of NA and Tb, affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer, resulting in the change of fluorescence intensity ratio. The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles. Furthermore, the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability, which is a promising portable sensor for practical applications.

  • RESEARCH ARTICLE
    Olga S. Arvaniti, Marilena E. Dasenaki, Alexandros G. Asimakopoulos, Niki C. Maragou, Vasilios G. Samaras, Korina Antoniou, Georgia Gatidou, Daniel Mamais, Constantinos Noutsopoulos, Zacharias Frontistis, Nikolaos S. Thomaidis, Athanasios S. Stasinakis
    Frontiers of Environmental Science & Engineering, 2022, 16(11): 148. https://doi.org/10.1007/s11783-022-1583-y

    ● Different advanced treatment processes were tested for ECs removal from wastewater.

    ● UV radiation showed low to moderate removal for 5 of the 38 micropollutants.

    ● Among tested membrane processes, nanofiltration showed the better performance.

    ● The use of PAC achieved high or partially removal for 31 out of the 38 compounds.

    ● The environmental and economical evaluation of a pilot-scale PAC unit is suggested.

    In this work, 38 different organic emerging contaminants (ECs), belonging to various chemical classes such as pharmaceuticals (PhCs), endocrine-disrupting chemicals (EDCs), benzotriazoles (BTRs), benzothiazoles (BTHs), and perfluorinated compounds (PFCs), were initially identified and quantified in the biologically treated wastewater collected from Athens’ (Greece) Sewage Treatment Plant (STP). Processes already used in existing STPs such as microfiltration (MF), nanofiltration (NF), ultrafiltration (UF), UV radiation, and powdered activated carbon (PAC) were assessed for ECs’ removal, under the conditions that represent their actual application for disinfection or advanced wastewater treatment. The results indicated that MF removed only one out of the 38 ECs and hence it was selected as pretreatment step for the other processes. UV radiation in the studied conditions showed low to moderate removal for 5 out of the 38 ECs. NF showed better results than UF due to the smaller pore sizes of the filtration system. However, this enhancement was observed mainly for 8 compounds originating from the classes of PhCs and PFCs, while the removal of EDCs was not statistically significant. Among the various studied technologies, PAC stands out due to its capability to sufficiently remove most ECs. In particular, removal rates higher than 70% were observed for 9 compounds, 22 were partially removed, while 7 demonstrated low removal rates. Based on our screening experiments, future research should focus on scaling-up PAC in actual conditions, combining PAC with other processes, and conduct a complete economic and environmental assessment of the treatment.

  • RESEARCH ARTICLE
    Yang Zhang, Zheng Peng, Zhaomin Dong, Mujie Wang, Chen Jiang
    Frontiers of Environmental Science & Engineering, 2022, 16(12): 152. https://doi.org/10.1007/s11783-022-1587-7

    ● China’s implementation of the SC was systematically studied.

    ● Implementation process of the SC can be roughly divided into three stages.

    ● DDT and HCH concentrations in the air have been steadily decreasing.

    ● China has safely disposed of 6352.1 tons of pesticide POPs.

    Persistent organic pollutants (POPs) are extremely harmful to the environment and human health; the Stockholm Convention on Persistent Organic Pollutants was therefore adopted by the international community in 2001 to eliminate or reduce the production, use, and emissions of POPs. China is the largest developing country that has signed the Stockholm Convention, and thus plays an important role in its implementation. This paper systematically studies the practice and achievements of China since it signed the Stockholm Convention 20 years ago. China has established an implementation guarantee system including institutions, implementation mechanisms, policies, law enforcement, and scientific and technological support. During the 20 years since the implementation of the Stockholm Convention, dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) concentrations in the air have been steadily decreasing, and Perfluorooctane sulfonic acid/Perfluorooctane sulfonyl fluoride (PFOS/PFOSF) concentrations in water bodies have decreased. In the past 20 years, China has safely disposed of 6352.1 tons of pesticide persistent organic pollutants and 36998 sets of electrical equipment containing polychlorinated biphenyls (PCBs), with a disposal rate of 100%. In the future, China will further strengthen the construction of persistent organic pollutant monitoring networks, scientific research, publicity, education, and international cooperation to improve environmental quality, providing a reference for other countries to implement the Stockholm Convention.

  • RESEARCH ARTICLE
    Jie Wu, Jian Lu, Jun Wu
    Frontiers of Environmental Science & Engineering, 2022, 16(11): 140. https://doi.org/10.1007/s11783-022-1575-y

    ● Organic matter content significantly affected adsorption of E2/EE2 on saline soil.

    ● EE2 possessed higher competition intensity for adsorption sites than E2.

    ● The adsorption of E2/EE2 on saline soil was a spontaneous exothermic process.

    ● Desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity.

    Soil organic matter content was the main driving factor affecting adsorption and desorption process of 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on saline soil. The adsorption and desorption of E2 and EE2 on three saline soils showed the similar behavior that soil with the highest organic content possessed the highest adsorption capacity and the lowest desorption capacity for E2 and EE2. The adsorption capacity of untreated soil samples (with organic matter) was larger than that of soil samples without organic matter. For soil with the largest adsorption capacity, adsorption capacity of E2/EE2 on the untreated soil and soil colloid (with organic matter) respectively reached 0.15/0.30 μg/g and 0.16/0.33 μg/g while the soil and soil colloid without organic matter hardly adsorbed pollutants. The adsorption capacity of E2/EE2 at the initial concentration of 100 μg/L was 25/15 times higher than that at the initial concentration of 5 μg/L. E2 and EE2 had the same adsorption sites on saline soil while EE2 possessed higher competition intensity for adsorption sites than E2. Pseudo-first-order model (R2 = 0.995–0.986) and Langmuir model (R2 = 0.989–0.999) could better fit the adsorption process of E2 or EE2. The thermodynamic study further showed that the adsorption of E2/EE2 on saline soil was a spontaneous exothermic process. The desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity to possibly exert potential risk to the groundwater. The variation of the salinity led to the variation of soil organic carbon which subsequently changed the adsorption and desorption behaviors of endocrine disrupting chemicals in coastal saline soil. This study provides a new insight on the interfacial behavior of endocrine disrupting chemicals on saline soil.

  • RESEARCH ARTICLE
    Heidelore Fiedler, Mohammad Sadia, Thomas Krauss, Abeer Baabish, Leo W.Y. Yeung
    Frontiers of Environmental Science & Engineering, 2022, 16(10): 132. https://doi.org/10.1007/s11783-022-1541-8

    ● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk.

    ● All other perfluoroalkane substances had median values of zero (101 samples).

    ● Branched PFOS recommended to be analyzed separately from linear isomer.

    ● PFOS and PFOA showed differentiated regional and income distribution.

    ● Human health risk assessment values not yet available at global level.

    Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C4–C11; except PFOA) or could not be quantified in any sample (sulfonic acids, C4–C10, and long-chain carboxylic acids, C12–C14). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.

  • RESEARCH ARTICLE
    Meng Zhu, Yuhuan He, Xiaobao Wei, Haoran Qi, Yunpeng Zhang, Yijun Zhang, Ruyi Yang, Yongming Luo
    Frontiers of Environmental Science & Engineering, 2022, 16(9): 115. https://doi.org/10.1007/s11783-022-1547-2

    • DPAA sorption followed pseudo-secondary and intra-particle diffusion models.

    • Chemical bonding and intra-particle diffusion were dominant rate-limiting steps.

    • DPAA simultaneously formed inner- and outer-sphere complexes on siderite.

    • DPAA predominantly formed occluded inner-sphere complexes on magnetite.

    • Bidentate binuclear bond was identified for DPAA on siderite and magnetite.

    Diphenylarsinic acid (DPAA) is both the prime starting material and major metabolite of chemical weapons (CWs). Because of its toxicity and the widespread distribution of abandoned CWs in burial site, DPAA sorption by natural Fe minerals is of considerable interest. Here we report the first study on DPAA sorption by natural magnetite and siderite using macroscopic sorption kinetics, sequential extraction procedure (SEP) and microscopic extended X-ray absorption fine-structure spectroscopy (EXAFS). Our results show that the sorption pseudo-equilibrated in 60 minutes and that close to 50% and 20%–30% removal can be achieved for magnetite and siderite, respectively, at the initial DPAA concentrations of 4–100 mg/L. DPAA sorption followed pseudo-secondary and intra-particle diffusion kinetics models, and the whole process was mainly governed by intra-particle diffusion and chemical bonding. SEP and EXAFS results revealed that DPAA mainly formed inner-sphere complexes on magnetite (>80%), while on siderite it simultaneously resulted in outer-sphere and inner-sphere complexes. EXAFS analysis further confirmed the formation of inner-sphere bidentate binuclear corner-sharing complexes (2C) for DPAA. Comparison of these results with previous studies suggests that phenyl groups are likely to impact the sorption capacity and structure of DPAA by increasing steric hindrance or affecting the way the central arsenic (As) atom maintains charge balance. These results improve our knowledge of DPAA interactions with Fe minerals, which will help to develop remediation technology and predict the fate of DPAA in soil-water environments.

  • RESEARCH ARTICLE
    Shengqi Zhang, Chengsong Ye, Wenjun Zhao, Lili An, Xin Yu, Lei Zhang, Hongjie Sun, Mingbao Feng
    Frontiers of Environmental Science & Engineering, 2022, 16(7): 93. https://doi.org/10.1007/s11783-021-1501-8

    • Oxidation of methotrexate by high-valent metal-oxo species was first explored.

    • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0.

    • Ketonization and cleavage of peptide bond were two initial reaction pathways.

    • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals.

    • The less biodegradable products exhibited developmental and acute/chronic toxicity.

    Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M−1 s−1) than Mn(VII) (3.01 M−1 s−1) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.

  • RESEARCH ARTICLE
    Zhichao Shen, Lu Zhan, Zhenming Xu
    Frontiers of Environmental Science & Engineering, 2022, 16(8): 103. https://doi.org/10.1007/s11783-022-1524-9

    • New method of mineralizing PFCs was proposed.

    • Activated carbon was regenerated while mineralizing PFCs.

    • Molten NaOH has good mineralization effect on PFOS and PFBS.

    Current study proposes a green regeneration method of activated carbon (AC) laden with Perfluorochemicals (PFCs) from the perspective of environmental safety and resource regeneration. The defluorination efficiencies of AC adsorbed perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonate (PFBS) using three molten sodium salts and one molten alkali were compared. Results showed that defluorination efficiencies of molten NaOH for the three PFCs were higher than the other three molten sodium salts at lower temperature. At 700°C, the defluorination efficiencies of PFOS and PFBS using molten NaOH reached to 84.2% and 79.2%, respectively, while the defluorination efficiency of PFOA was 35.3%. In addition, the temperature of molten salt, the holding time and the ratio of salt to carbon were directly proportional to the defluorination efficiency. The low defluorination efficiency of PFOA was due to the low thermal stability of PFOA, which made it difficult to be captured by molten salt.The weight loss range of PFOA was 75°C–125°C, which was much lower than PFOS and PFBS (400°C–500°C). From the perspective of gas production, fluorine-containing gases produced from molten NaOH-treated AC were significantly reduced, which means that environmental risks were significantly reduced. After molten NaOH treatment, the regenerated AC had higher adsorption capacity than that of pre-treated AC.